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At least 271 records · Page 15

Flux Synthesis of Lattice‐Engineered Rutile Solid Solutions for Acidic Oxygen Evolution

Developing efficient and stable electrocatalysts for the acidic oxygen evolution reaction (OER) is vital for advancing proton exchange membrane water electrolysis (PEMWE) technologies. Here, in this study, we report a flux synthesis of nitrogen-doped Ti–Ru rutile-type solid-solution oxides (M-TiRu 4 ) using molten NaNO 3 as the flux medium. The flux medium promotes the low-temperature conversion of TiN to rutile TiO 2 , while in situ-formed RuO 2 nanoparticles facilitate lattice templating and couple with interfacial ion migration, enabling the formation of homogeneous solid solutions with abundant lattice heterogeneity. Simultaneously, nitrogen atoms are stably incorporated into the lattice of solid solutions, inducing bandgap narrowing, which enhances electronic conductivity. The developed M-TiRu 4 catalyst exhibits exceptional acidic OER performance, delivering a low overpotential of 194 mV at 10 mA cm −2 , superior durability over 600 h, and a Ru mass activity 7.8 times that of commercial RuO 2 . At the device level, M-TiRu 4 enables PEMWE operation at 1.64 V @ 2 A cm −2 and maintains stable performance at 500 mA cm −2 for 200 h with a minimal degradation rate of 20 µV h −1 . This work demonstrates a robust approach for designing high-performance, durable acidic OER catalysts via synergistic lattice and electronic structure engineering, paving the way for next-generation water-splitting technologies.

Wang, Fan [Univ. of Tennessee, Knoxville, TN (Unit↗

Studying Transient Phenomena in Thin Films with Reinforcement Learning

Neutron reflectometry has long been a powerful tool to study the interfacial properties of energy materials. Recently, time-resolved neutron reflectometry has been used to better understand transient phenomena in electrochemical systems. Those measurements often comprise a large number of reflectivity curves acquired over a narrow q range, with each individual curve having lower information content compared to a typical steady-state measurement. In this work, we present an approach that leverages existing reinforcement learning tools to model time-resolved data to extract the time evolution of structure parameters. Further, by mapping the reflectivity curves taken at different times as individual states, we use the Soft Actor-Critic algorithm to optimize the time series of structure parameters that best represent the evolution of an electrochemical system. We show that this approach constitutes an elegant solution to the modeling of time-resolved neutron reflectometry data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visualizing the SEI formation between lithium metal and solid-state electrolyte

The solid electrolyte interphase (SEI) is regarded as the most important factor affecting the durability of lithium-metal anode in all-solid-state batteries (ASSBs). Despite its significance, the nucleation and growth mechanism of SEI is not yet well understood. Here, we elucidate the thermodynamics and kinetics governing SEI formation at the Li|β-Li 3 PS 4 interface at the atomic scale via thermodynamic phase equilibrium analysis and machine-learning-potential-assisted molecular dynamics (MD) simulations. An accurate moment tensor potential using the machine-learning method is developed for a reactive model of Li|β-Li 3 PS 4 . This potential enabled us to perform large-scale MD simulations with the model size expanded to the experimental dimensions (~40 nm) while maintaining the same level of accuracy as density functional theory calculations. The results reveal a four-stage evolution process at the Li|β-Li 3 PS 4 interface, namely (i) fast ion diffusion, (ii) nucleation, (iii) Li 2 S growth, and (iv) stabilization. Notably, we demonstrate that the SEI can be categorized into crystalline and amorphous regions. The simulated SEI thickness, structure, and composition closely match experimental findings, validating the accuracy of the MD simulations. We further disclose the significant impact of ion diffusion kinetic limitations on the phase formation and crystallization of interfacial products. Furthermore, we shed light on the detailed potential energy (PE) distribution of lithium along the direction perpendicular to the interface. Finally, this information is crucial for better understanding interfacial ion mobility.

25 ENERGY STORAGE↗

Cations Enhance Hydride Transfer to Noncatalytic Metals in Concentrated Alkaline Electrolytes

Alkali metal cations are known to influence the kinetics of the hydrogen evolution reaction (HER), acting as either promoters or inhibitors to the rate-determining step depending on the metal surface, local pH, and cation concentration. Despite the importance of concentrated electrolytes for commercial electrochemical cells, the impact of cations on the HER in concentrated alkaline environments (>1 M) and in mixed cation systems remains poorly understood. Here, this study quantifies the HER kinetics at polycrystalline metal surfaces (Pt, Au, Cu, and Fe) and the equilibrium solvation environment in pure and mixed alkali metal hydroxide electrolytes at concentrations up to 3.0 M. Kinetic analyses of Au, Cu, and Fe revealed a positive cation-concentration-effect that was primarily driven by changes to the charge transfer coefficient. Multinuclear NMR spectroscopy examined the solvation of H 2 O/OH – species and the alkali cations as a function of (mixed) alkali cation concentration(s), and demonstrated rapid exchange between solvent, hydroxide, and solvated cations. Together, these findings support models where HER kinetics on noncatalytic metal surfaces in strongly alkaline conditions are primarily governed by the average polarization and polarizability of the metal/solution interface and that increasing cation activity continues to increase the transfer coefficient at metal-hydroxide concentrations up to 3.0 M. Electrolytes and additives which can outcompete weakly hydrated cations and disrupt the interfacial water structure are expected to suppress parasitic HER at electrodes for energy storage and electroplating.

Cations↗

Friction Stir Dovetailing of AA7099 to Steel with AA6061 Interlayer for Reduced Zn Embrittlement at Dissimilar Interface

Joining of high strength Al alloy (AA7099) to steel (rolled homogeneous armor) with and without AA6061 interlayer was achieved using a friction stir dovetailing (FSD) method. Detailed investigations were conducted to establish correlations between mechanical performance and microstructural evolution of FSD joints. Lap shear tensile testing revealed that incorporation of the AA6061 interlayer combined with tailored processing methodology significantly improved both mechanical interlocking and load transmission across the dovetail interface. Following incorporation of the interlayer, the maximum load carrying capacity and peak extension (of the AA7099/AA6061/steel joint) are 60% and 210% higher, respectively, than results obtained from an AA7099/steel joint without an interlayer. Without an AA6061 interlayer, formation of zinc rich intermetallic compounds led to brittle interfacial failure of the AA7099-steel FSD joint. Incorporation of novel tool and joint configuration eliminated asymmetric joint performance as a function of loading direction, which is generally observed in friction stir lap welding. The efficacy of the use of an AA6061 interlayer in joining AA7099 to steel was demonstrated through mechanical testing as well as high resolution analytical electron microscopy characterization.

Dissimilar metal joining, Friction stir dovetailin↗

Pulsed laser deposition and structural evolution of BaF 2 nanolayers in Eu-doped BaF 2 /Al 2 O 3 layered optical nanocomposite thin films

Here, we have developed a pulsed laser deposition (PLD) geometry for the growth of uniform BaF 2 nanoscale thin films, through control of the deposition conditions. Our goal is to use the BaF 2 layers with controllable structure as component layers in layered optical nanocomposites. The structure of the BaF 2 nanolayer evolves as a function of the layer thickness: BaF 2 grows via a layer-by-layer growth mode on Al 2 O 3 ; the layers are amorphous for a thickness < 3 nm, and then become nanocrystalline as the layer thickness increases. The BaF 2 nanocrystals have an FCC crystal structure with a weak < 111 > texture that becomes stronger for thicker films. We then demonstrate that our BaF2 films can be introduced into layered Al 2 O 3 /BaF 2 /EuO x nanocomposite films, which allows for control of the relative position of the Eu ions and the BaF 2 layer. Cross-section samples of the multilayered films show interfacial intermixing between the layers, which is related to implantation during the PLD process. This intermixing enables the incorporation of Eu ions into BaF 2 layers and form a thin Eu-doped BaF 2 nanolayer at the interface. The layered nanocomposite films show photoluminescence (PL) emission from Eu 3+ ions, and the PL intensity changes can be correlated with the crystallinity and crystal size changes in the BaF 2 layer. Our results provide guidance for achieving thin film nanocomposite materials with controllable structure and photoluminescence behavior for light emitting diodes, photovoltaics and other optical applications.

36 MATERIALS SCIENCE↗

Facile Interfacial Reduction Suppresses Redox Chemical Expansion and Promotes the Polaronic to Ionic Transition in Mixed Conducting (Pr,Ce)O 2−δ Nanoparticles

Mixed ionic/electronic conductors (MIECs) are essential components of solid-state electrochemical devices, such as solid oxide fuel/electrolysis cells. For efficient performance, MIECs are typically nanostructured, to enhance the reaction kinetics. However, the effect of nanostructuring on MIEC chemo-mechanical coupling and transport properties, which also impact cell durability and efficiency, has not yet been well understood. Here, in this work, Pr 0.2 Ce 0.8 O 2−δ (PCO20) nanopowders were prepared by coprecipitation, then sintered in a modified dilatometer at three different temperatures (600, 725, and 850 °C) for microstructure evolution, resulting in three samples with different average particle sizes (23, 30, and 53 nm). The chemical strain and electronic/ionic conductivity were then measured simultaneously on stable nanostructures in four isotherms from 550 to 400 °C with steps in pO 2 (1 to 10 –4 atm O 2 ). A microcrystalline bar was prepared and measured for comparison. Particle size reduction led to a monotonically decreasing isothermal redox chemical strain, confirmed by in situ high-temperature, controlled-atmosphere XRD measurements. The corresponding conductivity measurements provided defect chemical insight into the particle size-dependent chemical expansion behavior. The significant weakening of the pO 2 dependence and decreased activation energy for electrical conduction with decreasing particle size indicated a decrease in the reduction enthalpy of PCO, shifting the transition from (Pr) polaronic to ionic behavior to higher pO 2 . STEM-EELS measurements confirmed the majority of Pr was reduced to 3+ in the nanoparticles, while Ce remained 4+. These results demonstrate suppression of deleterious chemical expansion and tailoring of the dominant charge carrier simply through controlling the particle size, providing insights for MIEC microstructural design.

ceria↗

Effect of Propagating Dopant Reactivity on Lattice Oxygen Loss in LLZO Solid Electrolyte Contacted with Lithium Metal

Lithium lanthanum zirconium oxide (LLZO) is widely known as the most stable solid electrolyte against lithium metal electrodes. This thermodynamic stability can be lost by the presence of dopants which are required to stabilize the cubic phase of LLZO and can be reduced by lithium metal. However, the role of oxygen in such reactions is taken for granted. In this work, the reduction of Nb-substituted LLZO (Nb-LLZO) is explored by Li metal and shows that interfacial reactions propagate and lead to the decomposition with substantial Nb 5+ reduction deep into the bulk electrolyte. Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy and thermogravimetric analyses show much of the reduction is due to oxygen vacancies formed, leading to increased electronic conductivity mapped with conductive Atomic Force Microscopy. Density functional theory calculations indicate oxygen release is favored by increased excess lithiation of Nb-LLZO. Electrochemical impedance of polycrystalline Nb-LLZO shows the continuous evolution of ionically resistive interphases near the lithium metal interface with Nb-LLZO while single crystals show little reactivity at room temperature and self-limiting reduction at 60°C. This work underlines the role of grain boundaries in propagating destructive solid electrolyte reactions and highlights previously unseen mechanisms involving lattice oxygen in LLZO.

Li metal, solid-state electrolytes↗

Unveiling the nucleation and growth of Zr oxide precipitates in internally oxidized Nb3Sn superconductors

We report on atomic-scale analyses of nucleation and growth of Zr oxide precipitates and the microstructural evolution of internally oxidized Nb3Sn wires for high-field superconducting magnet applications, utilizing atom probe tomography (APT), transmission electron microscopy (TEM), and first-principles calculations. APT analyses reveal that oxygen and zirconium are already segregated at grain boundaries (GBs) in the unreacted Nb-1Zr-4Ta (at%) alloy prior to forming Nb3Sn through reacting the Nb alloy with Sn and SnO2. After forming Nb3Sn, Zr oxide precipitates nucleate both at the Nb3Sn/Nb heterophase interfaces and in the Nb3Sn grains, driven by the small solubilities of Zr and O in Nb3Sn compared to their value in Nb. A high number density (Nv) of Zr oxide nanoprecipitates is observed in the Nb3Sn layers, ∼10 23 m −3 , with a mean diameter <10 nm for a heat treatment at 625 °C. Quantitative APT and TEM analyses of the Zr oxide precipitates in the reacted Nb3Sn layers elucidate details of the nucleation, growth, and coarsening processes of the Zr oxide precipitates in Nb3Sn. First-principles calculations and classical nucleation theory are employed to study the nucleation of Zr oxide precipitates in Nb3Sn and to estimate the maximum energy barrier and critical radius for nucleation. Our research unveils the kinetic pathways for nucleation and growth of Zr oxide precipitates and the microstructural evolution of Nb3Sn layers, which helps to understand and improve the superconducting properties of internally oxidized Nb3Sn wires for use in high-field superconducting magnets. •We investigated the nucleation and growth of Zr oxide nanoprecipitates in Nb3Sn superconductors for magnet applications.•APT and TEM analyses reveals the nucleation and growth process of Zr oxide precipitates in Nb3Sn layers.•Classical nucleation theory with DFT is employed to describe the nucleation process of Zr oxide precipitates in Nb3Sn.•We find that the interfacial reactions at Nb/Nb3Sn interface play a critical role in the nucleation of Zr oxide precipitates.•Current study provides a pathway to improve the properties of internally oxidized Nb3Sn superconducting wires.

43 PARTICLE ACCELERATORS↗

Sensitivity of cellular automata grain structure predictions for high solidification rates

Understanding as-solidified grain structure development during constrained (G 0) alloy solidification conditions is a necessary component of understanding the larger process-microstructure relationships during additive manufacturing (AM) processing. This study applies a cellular automata (CA) model, for static solidification velocities and thermal gradients on the order of those expected in AM melt pools, to investigate grain shape development across ranges of input parameters governing temperature field evolution, nucleation, and growth. Variation in nucleated grain shape from columnar to equiaxed as a function of thermal gradient and nucleation density is modeled with CA and verified against the established transition model of Hunt and Gaumann. Furthermore, while thermal conditions and nucleation density are shown to have the largest roles on microstructure development, the sensitivity of grain structure was very unevenly distributed across parameter space. In particular, it was found that microstructure is very sensitive to mean nucleation undercooling and the interfacial response function in process space regimes near grain structure transitions, but entirely controlled by a combination of thermal gradient, solidification velocity, and nucleation density away from such transitions. The understanding of grain shape sensitivity obtained through CA modeling, particularly at large thermal gradient and nucleation density, will be necessary for accurate microstructure prediction during the extreme processing conditions and large input parameter uncertainty common to AM.

36 MATERIALS SCIENCE↗

Nanoscale visualization of the thermally driven evolution of antiferromagnetic domains in FeTe thin films

Antiferromagnetic order, being a ground state of a number of exotic quantum materials, is of immense interest both from the fundamental physics perspective and for driving potential technological applications. For a complete understanding of antiferromagnetism in materials, nanoscale visualization of antiferromagnetic domains, domain walls, and their robustness to external perturbations is highly desirable. Here, we synthesize antiferromagnetic FeTe thin films using molecular-beam epitaxy. We visualize local antiferromagnetic ordering and domain formation using spin-polarized scanning tunneling microscopy. From the atomically resolved scanning tunneling microscopy topographs, we calculate local structural distortions to find a high correlation with the distribution of the antiferromagnetic order. This is consistent with the monoclinic structure in the antiferromagnetic state. Interestingly, we observe a substantial domain-wall change by small temperature variations, unexpected for the low-temperature changes used compared to the much higher antiferromagnetic ordering temperature of FeTe. This is in contrast to electronic nematic domains in the cousin FeSe multilayer films, where we find no electronic or structural change within the same temperature range. Further, our experiments provide the atomic-scale imaging of perturbation-driven magnetic domain evolution simultaneous with the ensuing structural response of the system. The results reveal surprising thermally driven modulations of antiferromagnetic domains in FeTe thin films well below the Néel temperature.

36 MATERIALS SCIENCE↗

Evolution of elastic and thermal properties of cementitious composites containing micro-size lightweight fillers after exposure to elevated temperature

This work studies the evolution of elastic and thermal properties of cementitious composites containing micro-size lightweight fillers after exposure to elevated temperatures (up to 800 °C). A multiscale investigation is carried out to study the thermal degradation of cementitious composite materials at multiple scale levels: at cement past level, the dehydration kinetics of cement hydrates (i.e., C–S–H, CH and aluminate hydrates) and development of microcracks are studied as functions of exposure temperatures. The damage mechanism of the inclusion phases and damages within the interfacial transition zone (ITZ) under elevated temperature are also investigated. In addition, the change of mechanical (i.e., elastic moduli, compressive strengths) and thermal (thermal conductivities) properties are measured as functions of the exposure temperature. Based on the experimental studies, a multiscale thermal degradation model is developed where the thermal degradations of cement paste (including water composition, porosity, and solid phase changes), inclusion phases, and the interfaces are captured through a multiscale sub-stepping homogenization scheme. The thermal degradation model is validated through multiple sets of experimental data. Finally, the influence of key parameters including the particle size distribution of the inclusions, the chemical composition, as well as the effects of ITZ damage are studied.

36 MATERIALS SCIENCE↗

Mathematical modeling of novel porous transport layer architectures for proton exchange membrane electrolysis cells

Thin foil based porous transport layers (PTLs) that contain highly structured pore arrays have shown promise as anode PTLs in proton exchange membrane electrolysis cells. These novel PTLs, fabricated with advanced manufacturing techniques, produce thin, tunable, multifunctional layers with reduced flow and interfacial resistances and high thermal and electric conductivities. To further optimize their design, it is important to understand their fundamental impact on the transport of protons, electrons, and liquid/vapor mixtures in the electrode. In this work, we develop a two-dimensional multiphysics model to simulate the coupled electrochemistry and multiphase transport in an electrolysis cell operated with the novel PTL architecture. The results show that larger pores improve access of water to the anode catalyst layer, which is beneficial for both the oxygen evolution reaction and membrane hydration. Larger pore sizes also improve oxygen gas transport from the catalyst layer, because generated oxygen gas is forced to travel in-plane through the anode catalyst layer until it reaches a pore opening that is connected to a channel. The discussed results confirm that the proposed thin foil based PTLs are fundamentally different from conventional PTLs, such as felts or layered meshes. The model developed in this work also provides generalizable insight into fundamental PEMEC phenomena, such as the competition between liquid and gas phase transport, membrane hydration and water management, and nonuniform electrochemical reactions, which are processes relevant to all PEMEC designs.

25 ENERGY STORAGE↗

Atom-by-atom imaging of moiré transformations in 2D transition metal dichalcogenides

Understanding the atomic-scale mechanisms that govern the structure of interfaces is critical across materials systems but particularly so for two-dimensional (2D) moiré materials. Here, we image, atom-by-atom, the thermally induced structural evolution of twisted bilayer transition metal dichalcogenides using in situ transmission electron microscopy. We observe low-temperature, local conversion of moiré superlattice into nanoscale aligned domains. Unexpectedly, this process occurs by nucleating a new grain within one monolayer, whose crystal orientation is templated by the other. The aligned domains grow through collective rotation of moiré supercells and hopping of 5|7 defect pairs at moiré boundaries. This provides mechanistic insight into the atomic-scale interactions controlling moiré structures and illustrates the potential to pattern interfacial structure and properties of 2D materials at the nanoscale.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nontrivial nanostructure, stress relaxation mechanisms, and crystallography for pressure-induced Si-I → Si-II phase transformation

Crystallographic theory based on energy minimization suggests austenite-twinned martensite interfaces with specific orientation, which are confirmed experimentally for various materials. Pressure-induced phase transformation (PT) from semiconducting Si-I to metallic Si-II, due to very large and anisotropic transformation strain, may challenge this theory. Here, unexpected nanostructure evolution during Si-I → Si-II PT is revealed by combining molecular dynamics (MD), crystallographic theory, generalized for strained crystals, and in situ real-time Laue X-ray diffraction (XRD). Twinned Si-II, consisting of two martensitic variants, and unexpected nanobands, consisting of alternating strongly deformed and rotated residual Si-I and third variant of Si-II, form {111} interface with Si-I and produce almost self-accommodated nanostructure despite the large transformation volumetric strain of -0.237. The interfacial bands arrest the {111} interfaces, leading to repeating nucleation-growth-arrest process and to growth by propagating {110} interface, which (as well as {111} interface) do not appear in traditional crystallographic theory.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A Dendrite-Resistant Sodium/Porous-Carbon Anode for Solid-State Batteries – Strategies and Challenges for Low-Pressure Operation

Sodium solid-state batteries (Na-SSB) have gained interest recently due to the abundance of Na over Li, but they still tend to fail due to dendrites under practical current densities and cycling capacities. To overcome this, Na-SSBs are frequently tested with impractically high applied pressure. In this work, a porous carbon interfacial layer is utilized in conjunction with Na-ß”-Al2O3 solid electrolytes to enable Na-cycling at milder cell pressures. This sodium/porous carbon layer enables improved solid-state Na cycling in symmetric cells, up to a current density of 10 mA cm-2 at 25 °C. Cycling up to 1 mAh cm-2 is challenging with low pressure, but 1 mAh cm-2 capacity can be reliably cycled at 1 mA cm-2 at an elevated temperature of 60 °C in symmetric cells. Finally, the evolution of the interface and sodium/carbon anode is evaluated with cryogenic ion-milling and cross-sectional imaging revealing that, depending on testing temperature, pressure, current density, and capacity, void formation, Na-extraction from porous carbon, delamination of the porous carbon matrix, or a combination of these occurs at the interface between Na-metal and BASE. Despite this, excellent dendrite resistance is achieved, and a full-cell design utilizing a Na-transition metal oxide cathode is still able to achieve an areal capacity of ~ 2.7 mAh cm-2 at 0.125 mA cm-2. This work demonstrates an alternative pathway toward a Na-metal anode for Na-SSBs without the requirement of excessive stack pressure.

low-cost↗

Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface

Rational construction of the electrode–solution interface where electrochemical processes occur is of paramount importance in electrochemistry. Efforts to gain better control and understanding of the interface have been hindered by lack of probing methods. Here, in this study, we show that the hydrogen evolution and oxidation reactions (HER/HOR) catalysed by platinum in base can be promoted by introduction of N-methylimidazoles at the platinum–water interface. In situ spectroscopic characterization together with simulations indicate that the N-methylimidazoles facilitate diffusion of hydroxides across the interface by holding the second layer of water close to platinum surfaces, thereby promoting the HER/HOR. We thus propose that the HER/HOR kinetics of platinum in acid and base is governed by diffusion of protons and hydroxides, respectively, through the hydrogen-bond network of interfacial water by the Grotthuss mechanism. Moreover, we demonstrate a 40% performance improvement of an anion exchange membrane electrolyser by adding 1,2-dimethylimidazole into the alkali fed into its platinum cathode.

36 MATERIALS SCIENCE↗

de Gennes Narrowing and Relationship between Structure and Dynamics in Self-Organized Ion-Beam Nanopatterning

Investigating the relationship between structure and dynamical processes is a central goal in condensed matter physics. Perhaps the most noted relationship between the two is the phenomenon of de Gennes narrowing, in which relaxation times in liquids are proportional to the scattering structure factor. Here, a similar relationship is discovered during the self-organized ion-beam nanopatterning of silicon using coherent x-ray scattering. However, in contrast to the exponential relaxation of fluctuations in classic de Gennes narrowing, the dynamic surface exhibits a wide range of behaviors as a function of the length scale, with a compressed exponential relaxation at lengths corresponding to the dominant structural motif—self-organized nanoscale ripples. These behaviors are reproduced in simulations of a nonlinear model describing the surface evolution. Our team suggests that the compressed exponential behavior observed here is due to the morphological persistence of the self-organized surface ripple patterns which form and evolve during ion-beam nanopatterning.

36 MATERIALS SCIENCE↗